Production of multi-enzyme granules

ABSTRACT

A process is presented for producing stable multi-enzyme containing granules. The process involves the steps of mixing a reversible competitive inhibitor with a first enzyme, adding a second incompatible enzyme, adding a carrier, extruding and granulating the resulting mixture and reducing the moisture content if necessary.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to enzyme granules containing at least twodifferent enzymes, to a process for their production and to the use ofthe granules in solid or liquid detergents and cleaning formulations.

2. Statement of Related Art

Enzymes, especially proteases, are widely used in detergents, washingaids and cleaning products. Normally, the enzymes are not used as puresubstances, but rather in the form of mixtures with a diluent/carriermaterial. If enzyme preparations of this type are added to conventionaldetergents, a considerable reduction in enzyme activity can occur duringstorage, especially if bleaching-active compounds are present.Application of the enzymes to carrier salts and simultaneous granulationin accordance with DE-OS 16 17 190 or by bonding using nonionicsurfactants in accordance with DE-OS 16 17 188 or aqueous solutions ofcellulose ethers in accordance with DE-OS 17 67 568 does not lead to asignificant improvement in storage stability because the sensitiveenzymes are generally situated on the surface of the carrier in mixturesof the type in question. Although the stability of the enzymes instorage can be significantly increased by coating the enzymes with orencapsulating them in the carrier material and converting them into therequired particle form by extrusion, pressing and spheronizing, asdescribed for example in DE-PS 16 17 232, in DE-OS 20 32 768 and inDE-ASS 21 37 042 and 21 37 043, corresponding enzyme preparations havepoor solubility properties. The undissolved particles can become caughtup in and thus soil the washing or pass into the wastewater withoutbeing used. Although the encapsulating compositions known from DE-OS 1803 099, which consist of a mixture of solid acids or acidic salts andcarbonates or bicarbonates and which disintegrate on addition of water,improve the solubility of the enzyme preparations, they are extremelysensitive to moisture and, accordingly, require additional protectivemeasures. Another disadvantage of the above-mentioned preparation isthat the enzymes can only be processed in the form of dry powders. Thefermenter broths typically accumulating in the enzyme production processcannot be used in this form, but have to be freed from water beforehand.

EP 168 526 describes enzyme granules which contain water-swellablestarch, zeolite and a water-soluble granulation aid. This documentproposes a production process for such formulations which overcomes theproblem mentioned above and which essentially comprises concentrating afermenter solution freed from insoluble constituents, introducing theadditives mentioned and granulating the resulting mixture. The processusing the additive mixture proposed therein is advantageously carriedout with fermentation solutions which have been concentrated to arelatively high dry matter content, for example of 55% by weight.

International patent application WO 92/11347 describes enzyme granulesfor use in granular detergents and cleaning compositions which contain2% by weight to 20% by weight of enzyme, 10% by weight to 50% by weightof swellable starch, 5% by weight to 50% by weight of water-solubleorganic polymer as granulation aid, 10% by weight to 35% by weight ofcereal flour and 3% by weight to 12% by weight of water. These additivesenable the enzyme to be processed without significant losses ofactivity. In addition, the storage stability of the enzymes in thegranules is also satisfactory.

As demonstrated by way of example by the documents cited above, a broadprior art exists in the field of the production of granular enzymepreparations, so that various possibilities for making up individualenzymes in particulate form are available to the expert. Unfortunately,the methods mentioned fail when two or more enzymes capable of reactingwith one another are to be incorporated in the same granule. Thisproblem arises in particular in connection with protease which, as aprotein-degrading enzyme, is of course capable of decomposing a secondenzyme and/or other enzyme present at the same time. If thisdecomposition process takes place during the production and/or storageof the enzyme granules, the effect of the second enzyme and/or otherenzymes under in-use conditions is no longer guaranteed.

Solutions to this problem have also been proposed in the prior art.Thus, according to International patent application WO 90/09440,two-enzyme granules are produced by coating a protease- andcellulose-containing core with a total of 10 layers (alternately stearicacid/palmitic acid glyceride and kaolin) the quantity of protectivecoating material in the Examples exceeding the quantity of core,subsequently applying a mixture of a second enzyme, a binder, a fillerand a granulation aid and, finally, applying an outer coating. Aproduction process such as this is unfavorable on account of the largeamount of separating material required between the enzyme-containingcore and the layer containing the second enzyme which lies further tothe outside. Another disadvantage can be that, under in-use conditions,the enzyme on the outside dissolves first, the second enzyme only beingreleased from the core at a later stage so that the two enzymes areunable to develop their effects at the same time.

Hitherto unpublished German patent application DE 43 29 463 describes aprocess for the production of multi-enzyme granules in which twoseparately prepared batches of granules differing in size and eachcontaining an enzyme are agglomerated in a subsequent co-granulationstep.

It is known from European patent application EP 304 332 thatenzyme-containing basic granules can be coated with powder-formcomponents containing a second enzyme. However, this method of producingmulti-enzyme granules often leads to inadequate stability of the secondenzyme present in the outer layer which, in addition, has to be preparedbeforehand in powder form--another disadvantage of this method. In thisvariant, too, the two enzymes are generally not released simultaneouslyin the wash or cleaning liquor.

DESCRIPTION OF THE INVENTION

Accordingly, the problem addressed by the present invention was toprovide a simple process for producing particulate enzyme preparationscontaining at least two different enzymes reacting with one anotherwhich would enable the enzymes to be incorporated in the multi-enzymegranules without any loss of activity and to remain therein instorage-stable manner. Surprisingly, this problem has been essentiallysolved by the use of a competitively reversibly inhibited enzyme in theform of an aqueous formulation which is mixed with more enzyme andadditives and extruded in the form of this mixture.

Accordingly, the present invention relates a process for the productionof enzyme granules containing at least two different enzymes by mixingan aqueous liquid containing a first enzyme, which may optionally be afermentation broth freed from insoluble constituents and concentrated,with a competitive inhibitor for this enzyme, subsequently mixing theprimary enzyme with the second enzyme or with further enzymes,incorporating an organic and/or inorganic carrier material, extrudingthe resulting mixture of enzymes and additives through a multiple-boredie followed by a cutting unit, optionally spheronizing the extrudate ina spheronizing unit and drying and, if desired, applying an optionallydye- and/or pigment-containing coating.

The present invention also relates to the use of the multi-enzymegranules obtainable in this way in detergents or cleaning compositions,more especially in particulate detergents or cleaning compositions.

The process according to the invention provides enzyme granules whichare suitable for incorporation in detergents and cleaning formulationsand which are characterized in that they contain at least two differentenzymes, more particularly enzymes which are capable of reacting withone another, i.e. which are not compatible with one another, inhomogeneous distribution. The enzymes incompatible with one another maybe incorporated together by the process according to the invention ingranules in which they are present in substantially homogeneous form,but do not adversely affect one another. A crucial requirement in thisregard is that the secondary enzyme should not be directly added to theconcentrated aqueous primary enzyme solution, instead the primary enzymeshould first be reversibly inactivated by a competitive inhibitor in theaqueous concentrate. Under in-use conditions, i.e. in water-containingwash or cleaning liquors, the inhibition of the primary enzyme iseliminated by the disintegration of the granule structure and by thedissolution of the inhibitor so that the primary and secondary enzymesdevelop their effects at more or less the same time. The primary enzymeis preferably protease while the secondary enzyme is preferably amylase,lipase, cellulase, hemicellulase, oxidase, peroxidase or mixturesthereof. The secondary enzyme may be incorporated in the primary enzymein liquid form, for example as a commercial concentrate, or in solidmade-up form, for example in the form of commercial granules.

The primary enzyme present in the enzyme granules produced in accordancewith the invention is, above all, protease obtained from microorganisms,such as bacteria or fungi. It may be obtained from suitablemicroorganisms by known fermentation processes which are described, forexample, in DE-OSS 19 40 488, 20 44 161, 21 01 803 and 21 21 397, inU.S. Pat. Nos. 3,632,957 and 4,264,738, in European patent applicationEP 006 638 and in International patent application WO 91/02792.Proteases are commercially available, for example, under the namesBLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym®or Maxapem®.

The primary enzyme is preferably present in the extrudates according tothe invention in quantities of 1% by weight to 6% by weight. If theenzyme granules according to the invention are a protease-containingformulation, their protease activity preferably amounts to between50,000 protease units (PU, as determined by the method described inTenside 7 (1970), 125) and 350,000 PU and, more particularly, to between100,000 PU and 250,000 PU per gram of enzyme granules.

The lipase suitable for use as the secondary enzyme or as a secondaryenzyme component in the process according to the invention may beobtained from Humicola lanuginosa, as described for example in Europeanpatent applications EP 258 068, EP 305 216 and EP 341 947, from Bacillusspecies, as described for example in International patent application WO91/16422 or in European patent application EP 384 717, from Pseudomonasspecies, as described for example in European patent applications EP 468102, EP 385 401, EP 375 102, EP 334 462, EP 331 376, EP 330 641, EP 214761, EP 218 272 or EP 204 284 or in International patent application WO90/10695, from Fusarium species as described, for example, in Europeanpatent application EP 130 064, from Rhizopus species as described, forexample, in European patent application EP 117 553, or from Aspergillusspecies as described, for example, in European patent application EP 167309. Suitable lipases are commercially obtainable, for example, underthe names Lipolase®, Lipozym®, Lipomax®, Amano® Lipase, Toyo Jozo®Lipase, Meito® Lipolase and Diosynth® Lipase. Lipase is preferably usedin the process according to the invention in such quantities that themulti-enzyme granules contain 1 KLU/g (Kilo Lipase Units per gramaccording to the Novo standard method based on the enzymatic hydrolysisof tributyrin, as described in Novo Nordisk publication AF 95) to 80KLU/g, preferably 1.5 KLU/g to 60 KLU/g and more preferably 2 KLU/g to30 KLU/g.

Multi-enzyme granules containing protease as the primary enzyme andamylase as the secondary enzyme are particularly suitable for use indishwashing detergents, particularly machine dishwashing detergents.Suitable amylases are commercially available, for example, under thenames Maxamyl® and Termamyl®. Amylase is preferably used in the processaccording to the invention in such quantities that the multi-enzymegranules contain 1 KNU/g (Kilo Novo Units per gram according to the Novostandard method, 1 KNU being the quantity of enzyme which degrades 5.26g of starch at pH 5.6/37° C., based on the method described by P.Bernfeld in S. P. Colowick and N. D. Kaplan, Methods in Enzymology, Vol.1, 1955, page 149) to 100 KNU/g, preferably 2 KNU/g to 60 KNU/g and morepreferably 5 KNU/g to 50 KNU/g.

The cellulase suitable for use as the secondary enzyme or as a secondaryenzyme component may be an enzyme obtainable from bacteria or fungiwhich has an optimum pH preferably in the mildly acidic to mildlyalkaline range of 6 to 9.5. Corresponding cellulases are known, forexample, from DE-OSS 31 17 250, 32 07 825, 32 07 847, 33 22 950 or fromEuropean patent applications EP 265 832, EP 269 977, EP 270 974, EP 273125 and EP 339 550. They are preferably used in such quantities that thefinal multi-enzyme granules have a cellulolytic activity of 50 CEVU/g(Cellulose Viscosity Units per gram based on the enzymatic hydrolysis ofcarboxymethyl cellulose at pH 9.0/40° C., as described in Novo Nordiskpublication AF 253) to 1250 CEVU/g and, preferably, 100 CEVU/g to 1000CEVU/g.

The production process according to the invention comprises mixing afirst enzyme which is present in liquid form, for example in the form ofan aqueous fermentation broth optionally freed from insolubleconstituents, and which preferably has a water content below 35% byweight and, more particularly, from 5% by weight to 30% by weight with acompetitive inhibitor for this enzyme. Such inhibitors includepolyhydric alcohols, more particularly glycerol, propylene glycol, aminoalcohols, for example mono-, di- and tri-ethanolamine and -propanolamineand mixtures thereof, lower carboxylic acids, for example as known fromEuropean patent applications EP 376 705 and EP 378 261, boric acid andalkali metal borates, boric acid/carboxylic acid combinations as known,for example, from European patent application EP 451 921, boric acidesters as known, for example, from International patent application WO93/11215 or from European patent application EP 511 456, boric acidderivatives as known, for example, from European patent application EP583 536, calcium salts, for example the calcium/formic acid combinationknown from European patent EP 28 865, magnesium salts as known, forexample, from European patent application EP 378 262 and/orsulfur-containing reducing agents as known, for example, from Europeanpatent applications EP 080 748 or EP 080 223. The substances mentionedare preferably used in quantities of 20% by weight to 60% by weight andpreferably in quantities of 35% by weight to 50% by weight, based on theresulting mixture of water-containing enzyme and inhibitor.

Suitable carrier materials for the enzyme mixture, which may beincorporated immediately afterwards, but more particularly only afteraddition of the secondary enzyme, are in principle any organic orinorganic powder-form substances which destroy or only reversiblydeactivate the enzymes to a negligible extent, if at all, and which arestable under extrusion conditions. Corresponding substances are, forexample, cellulose, maltodextrose, sucrose, invert sugar, glucose,starches, cereal flours, cellulose ethers, alkali metal alumosilicate,more particularly zeolite, layer silicate, for example bentonite orsmectite, and water-soluble inorganic or organic salts, for examplealkali metal chloride, alkali metal sulfate, alkali metal carbonate oralkali metal acetate, sodium or potassium being the preferred alkalimetals. A mixture of starch, cereal flour, powder-form cellulose andsucrose and, optionally, cellulose ether and alkali metal carbonate ispreferably used as the carrier material. If the secondary enzyme is usedin solid form, it is generally present in the form of a powder orgranules made up with such carrier materials. In one embodiment of theprocess according to the invention, there is no need in this case forthe separate addition of carrier material.

The starch suitable as the carrier material or as a component of thecarrier material is preferably corn starch, rice starch, potato starchor mixtures thereof, corn starch being particularly preferred. Starch ispreferably present in the carrier material for the enzyme mixture inquantities of 20 to 80% by weight and, more preferably, in quantities of25% by weight to 75% by weight, based on the carrier material as awhole. The sum total of the quantities of starch and flour is preferablynot more than 95% by weight and, more particularly, is between 60% byweight and 95% by weight. The cereal flour is in particular a productobtainable from wheat, barley, rye or oats or a mixture of these flours,whole-grain flours being preferred. A whole-grain flour in the contextof the invention is understood to be a flour which has not been fullyground and which has been produced from whole non-dehulled grains orwhich consists at least predominantly of such a product, the restconsisting of fully ground flour or starch. Commercially available wheatflours, such as Type 450 or Type 550, are preferably used. It is alsopossible to use ground products of the cereals leading to the starchesmentioned above providing steps are taken to ensure that the flours havebeen produced from whole grains. It is known that the flour component ofthe additive mixture significantly reduces the odor of the enzymepreparation to an extent considerably greater than that achieved byincorporating corresponding starches in the same quantities.Corresponding cereal flour is preferably present in the carrier materialfor the primary enzyme in quantities of 10% by weight to 35% by weightand, more preferably, in quantities of 15% by weight to 20% by weight.

Granulation aids may be present as additional constituents of thecarrier material, including for example cellulose or starch ethers, suchas carboxymethyl cellulose, carboxymethyl starch, methyl cellulose,hydroxyethyl cellulose, hydroxypropyl cellulose and correspondingcellulose mixed ethers, gelatine, casein, tragacanth or otherwater-soluble or readily water-dispersible oligomers or polymers ofnatural or synthetic origin. The synthetic water-soluble polymersinclude alkyl or alkenyl polyethoxylates, polyethylene glycols,polyacrylates, polymethacrylates, copolymers of acrylic acid with maleicacid or compounds containing vinyl groups, also polyvinyl alcohol,partly hydrolyzed polyvinyl acetate and polyvinyl pyrrolidone.Polyethylene glycols are preferably selected from those having averagemolecular weights of 200 to 3,000. If the granulation aids mentionedabove are those containing carboxyl groups, they are normally present inthe form of their alkali metal salts, more especially their sodiumsalts. Corresponding granulation aids may be present in the enzymecompounds suitable for the purposes of the invention in quantities of upto 10% by weight and, more particularly, in quantities of 0.5% by weightto 8% by weight, based on the multi-enzyme mixture to be extruded. Thedegree of substitution in carboxymethyl celluloses preferably used is inthe range from 0.8 to 0.95 because particularly strong granules areobtained where corresponding carboxymethyl celluloses are used orsmaller quantities are required to obtain granules of a certain strengththan where cellulose having a relatively low degree of substitution isused. In addition, by using the above-mentioned carboxymethyl cellulosewith a relatively high degree of substitution, a higher throughputthrough the extruder can be achieved in the extrusion step of thegranule production process. The degree of substitution of thecarboxymethyl cellulose is understood to be the number of etherifiedoxygen atoms bearing a carboxymethyl group per saccharide monomer of thecellulose.

The secondary enzyme present in solid or, preferably, liquid form may beadded to the primary enzyme afterwards or before addition of the carriermaterial or granulation aid. The other constituents of the secondaryenzyme optionally present in addition to the second enzyme are notcritical although--for the preferred use of the enzyme granulesaccording to the invention in detergents and cleaningcompositions--typical ingredients of detergents and cleaningcompositions or at least substances compatible therewith are preferablypresent. If the secondary enzyme is added in solid form, i.e. inadmixture with carriers or diluents, this added component preferablycontains inorganic salt, more particularly alkali metal sulfate and/orchloride, in quantities--based on the secondary enzyme preparation--of30% by weight to 80% by weight, fibrous or powder-form cellulose inquantities of 2 to 40% by weight and binders, more particularlydextrose, sucrose, polyvinyl alcohol and/or polyvinyl pyrrolidone, inquantities of 0.1% by weight to 15% by weight. Made-up enzyme granulescontaining the secondary enzyme may also be used in the productionprocess according to the invention. Accordingly, the particle containingthe second enzyme may be produced by an extrusion process as described,for example, in International patent application WO 92/11347 or inEuropean patent EP 168 526. Particulate secondary enzymes are preferablyproduced by pan granulation from an inorganic and/or organic carriermaterial and aqueous enzyme solution. A corresponding process usinginorganic salt and cellulose fibers in the carrier material and waterand/or a wax-like substance as binder is described, for example, inGerman patent DE 27 30 481.

The enzyme granules according to the invention are preferably producedfrom aqueous primary enzyme fermenter broths which are freed frominsoluble impurities, for example by microfiltration. Themicrofiltration is preferably carried out as crossflow microfiltrationusing porous tubes with micropores larger than 0.1 μm in size, flowrates of the concentrate solution of more than 2 m/s and a pressuredifference to the permeate side of less than 5 bar, as described, forexample in European patent application EP 200 032. The microfiltrationpermeate is then concentrated, preferably by ultrafiltration optionallyfollowed by vacuum evaporation. Concentration is preferably carried outin such a way that water contents of no more than 35% by weight areobtained. The concentrate is mixed with the secondary enzyme and a drypowder-form to granular mixture of the above-described carrier materialsor extrusion aids preferably prepared in advance, addition in thereverse order or simultaneous addition also being possible. Theseadditives are preferably selected from the carrier materials andextrusion aids mentioned in such a way that the multi-enzyme extrudateformed has an apparent density of 700 g/l to 1200 g/l. The water contentof the mixture to be extruded should be selected so that it can beconverted during compounding with stirring and beating tools intogranular particles non-tacky at room temperature and can be plasticallydeformed and extruded under relatively high pressures. The multi-enzymemixture is then processed in basically known manner in a kneader and anadjoining extruder to form a plastic, substantially homogeneous pastewhich can undergo an increase in temperature to between 40° C. and 60°C. and, more particularly, to between 45° C. and 55° C. as a result ofcompounding. The material leaving the extruder is passed through amultiple bore die followed by a cutting blade so that it is reduced tocylindrical particles of predetermined size. The diameter of the boresin the multi-bore die is best from 0.7 mm to 1.2 mm and preferably from0.8 mm to 1.0 mm. The length-to-thickness ratio of the extrudate ispreferably in the range from 0.9 to 1.1:1 and, more preferably, is1.0:1. The particles present in this form may then be directlyincorporated in detergents and cleaning compositions, optionally after adrying step. However, it has been found to be of advantage to spheronizethe cylindrical particles leaving the extruder and cutter, i.e. to roundthem off and to "deflash" them in suitable machines. A correspondingspheronizing process is described, for example, in DE-OSS 21 37 042 and21 37 043. It is carried out in a machine consisting of a cylindricalcontainer with stationary, fixed side walls and a friction platerotatably mounted on its base. Machines of this type are marketed underthe name of Marumerizer®. After spheronizing, the still moist sphericalparticles are dried continuously or in batches, preferably in afluidized bed dryer, at a temperature of preferably 35° C. to 50° C.and, more particularly, at a maximum product temperature of 45° C. to aresidual moisture content of 4% by weight to 10% by weight andpreferably 5% by weight to 8% by weight if they previously had higherwater contents. At this stage of the process, any dust-like fractionssmaller than 0.1 mm and, more particularly, 0.4 mm in size occurringduring the production of the extrudate and any coarse fractions largerthan 2 mm and, more particularly, 1.6 mm in size can be removed bysieving or air separation and optionally returned to the productionprocess. The extrusion process is preferably carried out in such a waythat the multi-enzyme extrudates formed have such a particle sizedistribution that less than 10% by weight and, more particularly, lessthan 2% by weight of the particles are smaller than 0.2 mm in diameter,10% by weight to 20% by weight of the particles are 0.2 mm to less than0.4 mm in diameter and 80% by weight to 90% by weight of the particlesare from 0.4 mm to less than 0.8 mm in diameter.

Substances for encapsulating and coating the extrudate particles may beadditionally introduced after or preferably during the drying process.To this end, the drying step is preferably carried out by spraying theenzyme-containing particles in a fluidized bed with a typical binderwhich, in its most simple form, may be water. Other suitable binders arenonionic surfactants and, more particularly, film formers selected fromthe water-soluble organic polymers mentioned above, for examplecarboxymethyl cellulose and/or polyethylene glycol, which may be used assuch or, more particularly, in the form of aqueous solutions. Inaddition, dyes or pigments may also be applied to the particles at theagglomeration stage in order to mask or modify any coloration present inthe particles which generally emanates from the enzyme concentrate.Titanium dioxide and calcium carbonate have proved to be particularlysuitable inert and physiologically safe pigments, being introducedsubsequently or preferably together with the binder in the form of anaqueous dispersion. The water introduced with the pigment dispersion orwith the binder is removed again during the drying step which is carriedout at the same time or which may have to be carried out at a laterstage.

It is readily possible by the process according to the invention toobtain multi-enzyme granules which have the enzyme activity for eachenzyme present theoretically expected from the activity of theindividual enzymes used. In general, more than 90% and, in particular,more than 95% of the expected activity is maintained.

The multi-enzyme granules obtainable in this way are preferably used forthe production of solid, above all particulate detergents or cleaningproducts which may be obtained simply by mixing the multi-enzymegranules with other components typically used in detergents or cleaningproducts. Surprisingly, however, multi-enzyme granules according to theinvention may also be incorporated in liquid or free-flowing andpaste-like, water-free or water-containing formulations in which themulti-enzyme granules are insoluble, a distinct increase in thestability of the enzymes in storage by comparison with enzymesintroduced in solution being obtained despite the simultaneous presenceof incompatible enzymes. The viscosity of liquid formulations such asthese is preferably in the range from 100 mPa·s to 60,000 mPa·s and maybe adjusted within wide limits through the concentration in which soapand solvents, for example, are used. Protease/amylase granules accordingto the invention in particular are preferably used in machinedishwashing detergents which are preferably marketed as compactedpowders with elevated apparent densities of, preferably, 750 to 1,000g/l or in tablet form. Corresponding tablets are preferably produced bymixing the multi-enzyme granules with all the other ingredients in amixer and tabletting the resulting mixture in conventional tabletpresses, for example eccentric presses or rotary presses, underpressures of 200·10⁵ Pa to 1500·10⁵ Pa. Breakage-resistant tablets whichstill dissolve sufficiently quickly under in-use conditions are readilyobtained in this way, typically with flexural strengths in excess of 150N. A correspondingly produced tablet preferably has a weight of 15 g to40 g and, more particularly, 20 g to 30 g for a diameter of 35 mm to 40mm.

For incorporation in particulate detergents and cleaning formulations,the enzyme granules preferably have average particle sizes of 0.9 mm to1.8 mm and, more preferably, in the range from 1.0 mm to 1.5 mm. Thegranules produced in accordace with the invention preferably containless than 5% by weight and, more preferably, at most 1% by weight ofparticles with sizes outside the 0.2 mm to 1.6 mm range.

The enzyme preparation obtained in accordance with the inventionconsists of substantially rounded dust-free particles which generallyhave an apparent density of around 650 to 1050 grams per liter and, moreparticularly, 700 to 880 grams per liter. The granules produced inaccordance with the invention are distinguished by very high stabilityin storage, particularly at temperatures above room temperature and athigh atmospheric humidity levels, which--although enzymes capable ofreacting with one another are present--generally exceeds even thestability in storage of individual enzymes made up separately from oneanother. This applies both to the enzyme granules according to theinvention and to the enzyme granules according to the inventionincorporated in particulate detergents or cleaning formulations. Anotheradvantage of the enzyme granules according to the invention is theirdissolving behavior under in-use conditions in the wash liquor in whichall the enzymes present can be simultaneously released and can developtheir cleaning effect. In a preferred embodiment, the granules accordingto the invention release at least 90% of their enzyme activity in waterat 25° C. within 3 minutes and, more particularly, within 70 seconds to2.5 minutes.

Detergents or cleaning formulations containing multi-enzyme granulesaccording to the invention or produced by the process according to theinvention may contain other typical ingredients of such formulationswhich do not undesirably interact with the enzymes. The multi-enzymegranules are preferably incorporated in detergents or cleaningformulations in quantities of 0.1% by weight to 5% by weight and, moreparticularly, in quantities of 0.5% by weight to 2.5% by weight.

It has surprisingly been found that enzyme granules having theproperties described above synergistically influence the effect ofcertain other ingredients of detergents and cleaning compositions andthat, conversely, the effect of the enzymes present in the multi-enzymegranules is synergistically enhanced by certain other detergentingredients. These effects occur in particular in the case of nonionicsurfactants, in the case of soil-releasing copolyesters, particularlythose containing terephthalic acid units, in the case of water-insolubleinorganic builders, in the case of water-soluble inorganic and organicbuilders, more particularly based on oxidized carbohydrates, in the caseof peroxygen-based bleaching agents, more particularly alkali metalpercarbonate, and in the case of synthetic anionic surfactants of thesulfate and sulfonate type, but only to a negligible extent, if at all,in the case of alkyl benzene sulfonates, so that the ingredientsmentioned are preferably used together with multi-enzyme granulesaccording to the invention.

In one preferred embodiment, a corresponding formulation containsnonionic surfactant selected from fatty alkyl polyglycosides, fattyalkyl polyalkoxylates, more particularly ethoxylates and/orpropoxylates, fatty acid polyhydroxyamides and/or ethoxylation and/orpropoxylation products of fatty alkyl amines, vicinal diols, fatty acidalkyl esters and/or fatty acid amides or mixtures thereof, moreparticularly in quantities of 2% by weight to 25% by weight.

Another embodiment of such formulations is characterized by the presenceof synthetic anionic surfactant of the sulfate and/or sulfonate type,more particularly fatty alkyl sulfate, fatty alkyl ether sulfate,sulfofatty acid esters and/or sulfofatty acid disalts, more particularlyin a quantity of 2% by weight to 25% by weight. The anionic surfactantis preferably selected from the alkyl or alkenyl sulfates and/or thealkyl or alkenyl ether sulfates in which the alkyl or alkenyl groupcontains 8 to 22 carbon atoms and, more particularly, 12 to 18 carbonatoms.

Suitable nonionic surfactants are the alkoxylates, more particularly theethoxylates and/or propoxylates, of saturated or mono- topolyunsaturated linear or branched alcohols containing 10 to 22 andpreferably 12 to 18 carbon atoms. The degree of alkoxylation of thealcohols is generally between 1 and 20 and preferably between 3 and 10.They may be prepared in known manner by reaction of the correspondingalcohols with the corresponding alkylene oxides. Derivatives of thefatty alcohols are particularly suitable, although their branched-chainisomers, particularly so-called oxoalcohols, may also be used for theproduction of suitable alkoxylates. Accordingly, the alkoxylates, moreparticularly the ethoxylates, of primary alcohols containing lineargroups, more particularly dodecyl, tetradecyl, hexadecyl or octadecylgroups and mixtures thereof are suitable. Corresponding alkoxylationproducts of alkyl amines, vicinal diols and carboxylic acid amides,which correspond to the alcohols mentioned in regard to the alkylmoiety, may also be used. Other suitable nonionic surfactants are theethylene oxide and/or propylene oxide insertion products of fatty acidalkyl esters, which may be produced by the process described inInternational patent application WO 90/13533, and the fatty acidpolyhydroxyamides which may be produced by the processes according toU.S. Pat. Nos. 1,985,424, 2,016,962 and U.S. Pat. No. 2,703,798 andInternational patent application WO 92/06984. So-called alkylpolyglycosides suitable for incorporation in the formulations accordingto the invention are compounds corresponding to the general formula(G)_(n) --OR¹ where R¹ is an alkyl or alkenyl group containing 8 to 22carbon atoms, G is a glycose unit and n is a number of 1 to 10.Corresponding compounds and their production are described, for example,in European patent applications EP 92 355, EP 301 298, EP 357 969 and EP362 671 or U.S. Pat. No. 3,547,828. The glycoside component (G)_(n) isan oligomer or polymer of naturally occurring aldose or ketose monomers,including in particular glucose, mannose, fructose, galactose, talose,gulose, altrose, allose, idose, ribose, arabinose, xylose and lyxose.The oligomers consisting of such glycoside-bonded monomers arecharacterized not only by the type but also by the number of sugarspresent in them, the so-called degree of oligomerization. The degree ofoligomerization n as an analytically determined quantity is generally abroken number, assuming a value of 1 to 10 and, in the case of theglycosides preferably used, a value below 1.5 and, more particularly,between 1.2 and 1.4. Glucose is the preferred monomer by virtue of itsready availability. The alkyl or alkenyl group R¹ of the glycosides alsopreferably emanates from readily available derivatives of renewable rawmaterials, more particularly from fatty alcohols, althoughbranched-chain isomers thereof, more particularly so-called oxoalcohols,may also be used for the production of suitable glycosides. Accordingly,primary alcohols containing linear octyl, decyl, dodecyl, tetradecyl,hexadecyl or octadecyl groups and mixtures thereof are particularlysuitable. Particularly preferred alkyl glycosides contain a cocofattyalkyl group, i.e. mixtures with--essentially--R¹ =dodecyl and R¹=tetradecyl.

Nonionic surfactant is preferably present in formulations containingmulti-enzyme granules according to the invention in quantities of 1 to30% by weight and, more preferably, in quantities of 1% by weight to 25%by weight.

The formulations in question may contain other surfactants instead of orin addition to those mentioned above, preferably synthetic anionicsurfactants of the sulfate or sulfonate type, in quantities ofpreferably not more than 20% by weight and, more preferably, inquantities of 0.1% by weight to 18% by weight, based on the formulationas a whole. Alkyl and/or alkenyl sulfates containing 8 to 22 carbonatoms, in which an alkali metal, ammonium or alkyl- orhydroxyalkyl-substituted ammonium ion is present as countercation, arementioned as particularly suitable synthetic anionic surfactants for usein such formulations. The derivatives of fatty alcohols containing inparticular 12 to 18 carbon atoms and branched-chain analogs thereof,so-called oxoalcohols, are preferred. The alkyl and alkenyl sulfates maybe produced in known manner by reaction of the corresponding alcoholcomponent with a typical sulfating agent, more particularly sulfurtrioxide or chlorosulfonic acid, and subsequent neutralization withalkali metal, ammonium or alkyl- or hydroxyalkyl-substituted ammoniumbases. Corresponding alkyl and/or alkenyl sulfates are preferablypresent in the formulations containing multi-enzyme granules accordingto the invention in quantities of 0.1% by weight to 20% by weight and,more preferably, in quantities of 0.5% by weight to 18% by weight.

Other suitable surfactants of the sulfate type are the sulfatedalkoxylation products of the alcohols mentioned, so-called ethersulfates. These ether sulfates preferably contain 2 to 30 and, morepreferably, 4 to 10 ethylene glycol groups per molecule. Suitableanionic surfactants of the sulfonate type include the α-sulfoestersobtainable by reaction of fatty acid esters with sulfur trioxide andsubsequent neutralization, more particularly the sulfonation productsderived from fatty acids containing 8 to 22 carbon atoms, preferably 12to 18 carbon atoms, and linear alcohols containing 1 to 6 carbon atomsand preferably 1 to 4 carbon atoms and the sulfofatty acids obtainabletherefrom by formal saponification.

Other optional surface-active ingredients are soaps, saturated fattyacid soaps, such as the salts of lauric acid, myristic acid, palmiticacid or stearic acid, and soaps derived from natural fatty acidmixtures, for example coconut oil, palm kernel oil or tallow fattyacids, being suitable. Soap mixtures of which 50% by weight to 100% byweight consist of saturated C₁₂₋₁₈ fatty acid soaps and up to 50% byweight of oleic acid soap are particularly preferred. Soap is preferablypresent in quantities of 0.1% by weight to 5% by weight. However, largerquantities of soap, generally up to 20% by weight, may also be present,particularly in liquid formulations containing multi-enzyme granulesaccording to the invention.

In another embodiment, a formulation containing multi-enzyme granulesaccording to the invention contains water-soluble and/or insolublebuilders selected in particular from alkali metal alumosilicate,crystalline alkali metal silicate with a modulus of more than 1,monomeric polycarboxylate, polymeric polycarboxylate and mixturesthereof, more particularly in quantities of 2.5% by weight to 60% byweight.

A formulation containing multi-enzyme granules according to theinvention preferably contains 20% by weight to 55% by weight ofwater-soluble and/or water-insoluble organic and/or inorganic builders.The water-soluble organic builders include in particular those from theclass of polycarboxylic acids, more particularly citric acid and sugaracids, and polymeric (poly)carboxylic acids, more particularly thepolycarboxylates obtainable by oxidation of polysaccharides according toInternational patent application WO 93/16110, polymeric acrylic acids,methacrylic acids, maleic acids and copolymers thereof which may alsocontain small quantities of polymerizable substances with no carboxylicacid functionality in copolymerized form. The relative molecular weightof the homopolymers of unsaturated carboxylic acids is generally between5,000 and 200,000 while the relative molecular weight of the copolymersis between 2,000 and 200,000 and preferably between 50,000 and 120,000,based on free acid. A particularly preferred acrylic acid/maleic acidcopolymer has a relative molecular weight of 50,000 to 100,000.Suitable, albeit less preferred, compounds of this class are copolymersof acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in whichthe percentage content of the acid is at least 50% by weight. Othersuitable water-soluble organic builders are terpolymers containing twocarboxylic acids and/or salts thereof as monomers and vinyl alcoholand/or a vinyl alcohol derivative or a carbohydrate as the thirdmonomer. The first acidic monomer or its salt is derived from amonoethylenically unsaturated C₃₋₈ carboxylic acid and preferably from aC₃₋₄ monocarboxylic acid, more particularly from (meth)acrylic acid. Thesecond acidic monomer or its salt may be a derivative of a C₄₋₈dicarboxylic acid, preferably a C₄₋₈ dicarboxylic acid, maleic acidbeing particularly preferred. In this case, the third monomeric unit isderived from vinyl alcohol and/or preferably an esterified vinylalcohol. Vinyl alcohol derivatives in the form of an ester ofshort-chain carboxylic acids, for example C₁₋₄ carboxylic acids, withvinyl alcohol are particularly preferred. Preferred terpolymers contain60% by weight to 95% by weight and, more particularly, 70% by weight to90% by weight of (meth)acrylic acid or (meth)acrylate, preferablyacrylic acid or acrylate, and maleic acid or maleate and 5% by weight to40% by weight and preferably 10% by weight to 30% by weight of vinylalcohol and/or vinyl acetate. Terpolymers in which the ratio by weightof (meth)acrylic acid or (meth)acrylate to maleic acid or maleate isbetween 1:1 and 4:1, preferably between 2:1 and 3:1 and more preferablybetween 2:1 and 2.5:1 are most particularly preferred. Both thequantities and the ratios by weight mentioned are based on the acids.The second acidic monomer or its salt may also be a derivative of anallyl sulfonic acid substituted in the 2-position by an alkyl group,preferably a C₁₋₄ alkyl group, or by an aromatic radical preferablyderived from benzene or benzene derivatives. Preferred terpolymerscontain 40% by weight to 60% by weight and, more particularly, 45 to 55%by weight of (meth)acrylic acid or (meth)acrylate, preferably acrylicacid or acrylate, 10% by weight to 30% by weight and preferably 15% byweight to 25% by weight of methallyl sulfonic acid or methallylsulfonate and, as the third monomer, 15% by weight to 40% by weight andpreferably 20% by weight to 40% by weight of a carbohydrate. Thiscarbohydrate may be, for example, a mono-, di-, oligo- orpolysaccharide, mono-, di- or oligosaccharides being preferred andsucrose being particularly preferred. Predetermined weak spots arepresumably incorporated in the polymer through the use of the thirdmonomer, being responsible for the ready biodegradability of thepolymer. These polymers may be prepared in particular by the processesdescribed in German patent DE 42 21 381 and in German patent applicationP 43 00 772.4 and generally have a relative molecular weight in therange from 1,000 to 200,000, preferably in the range from 200 to 50,000and more preferably in the range from 3,000 to 10,000. They may be usedin the form of aqueous solutions, preferably in the form of 30 to 50% byweight aqueous solutions, especially for the production of liquidformulations. All the polycarboxylic acids mentioned are generally usedin the form of their water-soluble salts, more particularly their alkalimetal salts.

The organic builders in question are preferably present in quantities ofup to 40% by weight, more preferably in quantities of up to 25% byweight and most preferably in quantities of 1% by weight to 5% byweight. Quantities near the upper limit mentioned are preferably used inpaste-form or liquid formulations, more particularly water-containingformulations, in which the multi-enzyme granules according to theinvention are present.

Suitable water-insoluble, water-dispersible inorganic builders are, inparticular, crystalline or amorphous alkali metal alumosilicates whichare used in quantities of up to 50% by weight, preferably in quantitiesof not more than 40% by weight and, in liquid formulations inparticular, in quantities of 1% by weight to 5% by weight. Among thesebuilders, detergent-quality crystalline alumosilicates, more especiallyzeolite NaA and optionally NaX, are particularly preferred. Quantitiesnear the upper limit mentioned are preferably used in solid particulateformulations. Suitable alumosilicates in particular contain no particleslarger than 30 μm in size, at least 80% by weight preferably consistingof particles less than 10 μm in size. Their calcium binding capacity,which may be determined in accordance with German patent DE 24 12 837,is in the range from 100 to 200 mg CaO per gram. Suitable substitutes orpartial substitutes for the alumosilicate mentioned are crystallinealkali metal silicates which may be present on their own or in the formof mixtures with amorphous silicates. The alkali metal silicatessuitable as builders in the formulations preferably have a molar ratioof alkali metal oxide to SiO₂ of less than 0.95 and, more particularly,in the range from 1:1.1 to 1:12 and may be present in amorphous orcrystalline form. Preferred alkali metal silicates are the sodiumsilicates, more particularly the amorphous sodium silicates, with amolar Na₂ O to SiO₂ ratio of 1:2 to 1:2.8. Amorphous alkali metalsilicates such as these are commercially available, for example, underthe name of Portil®. Those with a molar Na₂ O:SiO₂ ratio of 1:1.9 to1:2.8 may be produced by the process according to European patentapplication EP 0 425 427. They are preferably added as a solid and notin the form of a solution in the production process. Preferredcrystalline silicates which may be present individually or in the formof a mixture with amorphous silicates are crystalline layer silicateswith the general formula Na₂ Si_(x) O_(2x+1).yH₂ O, in which x--theso-called modulus--is a number of 1.9 to 4 and y is a number of 0 to 20,preferred values for x being 2, 3 or 4. Crystalline layer silicatescorresponding to this general formula are described, for example, inEuropean patent application EP 0 164 514. Preferred crystalline layersilicates are those in which x in the general formula mentioned assumesa value of 2 or 3. β- and δ-sodium disilicates (Na₂ Si₂ O₅.yH₂ O) areparticularly preferred, β-sodium disilicate being obtainable for exampleby the process described in International patent application WO91/08171. δ-Sodium silicates with a modulus of 1.9 to 3.2 may beprepared in accordance with Japanese patent applications JP 04/238 809or JP 04/260 610. Substantially water-free crystalline alkali metalsilicates corresponding to the above general formula, where x is anumber of 1.9 to 2.1, which have been prepared from amorphous alkalimetal silicates as described in European patent applications EP 0 548599, EP 0 502 325 and EP 0 452 428, may also be used in formulationscontaining multi-enzyme granules according to the invention. Anotherpreferred embodiment of formulations according to the invention ischaracterized by the use of a crystalline sodium layer silicate with amodulus of 2 to 3 which may be produced from sand and soda by theprocess according to European patent application EP 0 436 835.Crystalline sodium silicates with a modulus of 1.9 to 3.5 obtainable bythe process according to European patents EP 0 164 552 and/or EP 0 293753 are used in another preferred embodiment of detergents or cleaningformulations containing multi-enzyme granules according to theinvention. Their content of alkali metal silicates is preferably between1% by weight and 50% by weight and more preferably between 5% by weightand 35% by weight, based on water-free active substance. If alkali metalalumosilicate, more particularly zeolite, is present as an additionalbuilder, the alkali metal silicate content is preferably 1% by weight to15% by weight and more preferably 2% by weight to 8% by weight, based onwater-free active substance. In this case, the ratio by weight ofalumosilicate to silicate, based on water-free active substances, ispreferably 4:1 to 10:1. In formulations containing both amorphous andcrystalline alkali metal silicates, the ratio by weight of amorphousalkali metal silicate to crystalline alkali metal silicate is preferably1:2 to 2:1 and more preferably 1:1 to 2:1.

In addition to the inorganic builder mentioned, other water-soluble orwater-insoluble inorganic substances may be used in the formulationscontaining multi-enzyme granules according to the invention. Alkalimetal carbonates, alkali metal hydrogen carbonates and alkali metalsulfates and mixtures thereof are suitable in this regard. Thisadditional inorganic material may be present in quantities of up to 70%by weight, but is preferably absent altogether.

The formulations may additionally contain other ingredients typical ofdetergents and cleaning formulations. These optional ingredients includein particular bleaching agents, bleach activators, heavy metalcomplexing agents, for example aminopolycarboxylic acids,aminohydroxypolycarboxylic acids, polyphosphonic acids and/oraminopolyphosphonic acids, redeposition inhibitors, for examplecellulose ethers, dye transfer inhibitors, for example polyvinylpyrrolidone or polyvinyl pyridine-N-oxide, foam inhibitors, for exampleorganopolysiloxanes or paraffins, solvents and optical brighteners, forexample stilbene disulfonic acid derivatives. Formulations containingmulti-enzyme granules according to the invention contain up to 1% byweight and, more particularly, from 0.01% by weight to 0.5% by weight ofoptical brighteners, more particularly compounds from the class ofsubstituted4,4'-bis-(2,4,6-triamino-s-triazinyl)-stilbene-2,2'-disulfonic acids, upto 5% by weight and, more particularly, from 0.1% by weight to 2% byweight of heavy metal complexing agents, more particularly aminoalkylenephosphonic acids and salts thereof, up to 3% by weight and, moreparticularly, 0.5% by weight to 2% by weight of redeposition inhibitorsand up to 2% by weight and, more particularly, from 0.1% by weight to 1%by weight of foam inhibitors, the parts by weight mentioned being basedon the formulation as a whole.

Apart from water, solvents which are used in particular in liquidformulations containing multi-enzyme granules according to the inventionand which may also be present in the liquid primary and/or secondaryenzyme in the production process for the multi-enzyme granules accordingto the invention are preferably water-miscible solvents, including loweralcohols, for example ethanol, propanol, isopropanol and the isomericbutanols, glycerol, lower glycols, for example ethylene and propyleneglycol, and the ethers derived from the classes of compounds mentioned.The multi-enzyme granules are present in undissolved form, i.e. in solidgranular form, in these liquid formulations.

The typical enzyme stabilizers optionally present, particularly inliquid formulations according to the invention, include amino alcohols,for example mono-, di-, tri-ethanolamine and -propanolamine and mixturesthereof, lower carboxylic acids as known, for example, from Europeanpatent applications EP 376 705 and EP 378 261, boric acid or alkalimetal borates, boric acid/carboxylic acid combinations as known, forexample, from European patent application EP 451 921, boric acid estersas known, for example, from International patent application WO 93/11215or European patent application EP 511 456, boric acid derivatives asknown, for example, from European patent application EP 583 536, calciumsalts, for example the calcium/formic acid combination known fromEuropean patent EP 28 865, magnesium salts as known, for example, fromEuropean patent application EP 378 262 and/or sulfur-containing reducingagents as known, for example, from European patent applications EP 080748 or EP 080 223.

Suitable foam inhibitors include long-chain soaps, more particularlybehenic soap, fatty acid amides, paraffins, waxes, microcrystallinewaxes, organopolysiloxanes and mixtures thereof which may additionallycontain microfine, optionally silanized or otherwise hydrophobicizedsilica. For use in particulate formulations, these foam inhibitors arepreferably fixed to granular water-soluble carriers as described, forexample, in DE-OS 34 36 194, in European patent applications EP 262 588,EP 301 414, EP 309 931 or European patent EP 150 386.

In addition, a formulation containing multi-enzyme granules according tothe invention may contain redeposition inhibitors. The function ofredeposition inhibitors is to keep the soil detached from the fiberssuspended in the liquid and thus to prevent discoloration of the fibers.Redeposition inhibitors include water-soluble generally organiccolloids, for example the water-soluble salts of polymeric carboxylicacids, glue, gelatin, salts of ether carboxylic acids or ether sulfonicacids of starch or cellulose or salts of sulfuric acid esters ofcellulose or starch. Water-soluble polyamides containing acidic groupsare also suitable for this purpose. Soluble starch preparations andother starch products than those mentioned above, for example partlyhydrolyzed starch, may also be used. Sodium carboxymethyl cellulose,methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof arepreferably used.

Another embodiment of a formulation containing multi-enzyme granulesaccording to the invention contains bleaching agents based on peroxygen,more particularly in quantities of 5% by weight to 70% by weight, andoptionally bleach activators, more particularly in quantities of 2% byweight to 10% by weight. The bleaching agents in question are the percompounds generally used in detergents, such as hydrogen peroxide,perborate which may be present as tetrahydrate or monohydrate,percarbonate, perpyrophosphate and persilicate which are generallypresent as alkali metal salts, more particularly sodium salts. Thesebleaching agents are preferably present in detergents containingmulti-enzyme granules according to the invention in quantities of up to25% by weight, more preferably in quantities of up to 15% by weight andmost preferably in quantities of 5% by weight to 15% by weight, based onthe detergent as a whole. The optional bleach activators include the N-or O-acyl compounds normally used, for example polyacylatedalkylenediamines, more particularly tetraacetyl ethylenediamine,acylated glycol urils, more particularly tetraacetyl glycol uril,N-acylated hydantoins, hydrazides, triazoles, urazoles,diketopiperazines, sulfuryl amides and cyanurates, also carboxylicanhydrides, more particularly phthalic anhydride, carboxylic acidesters, more particularly sodium isononanoyl phenol sulfonate, andacylated sugar derivatives, more particularly pentaacetyl glucose. Toavoid interaction with the per compounds in storage, the bleachactivators may have been coated or granulated in known manner withshell-forming substances, tetraacetyl ethylenediamine with mean particlesizes of 0.01 mm to 0.8 mm granulated with carboxymethyl cellulose andobtainable, for example, by the process described in European patent EP037 026 and/or granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazineobtainable by the process described in German patent DD 255 884 beingparticularly preferred. These bleach activators are preferably presentin detergents in quantities of up to 8% by weight and, moreparticularly, in quantities of 2% by weight to 6% by weight, based onthe detergent as a whole.

Finally, another embodiment of a formulation containing multi-enzymegranules according to the invention is characterized by the presence ofsoil release agents based on copolyesters of dicarboxylic acids andglycols which may be present in particular in quantities of 0.01 to 5%by weight. Soil release agents which are particularly effective byvirtue of their chemical similarity to polyester fibers, but which arealso capable of developing the required effect in fabrics of othermaterials are copolyesters containing dicarboxylic acid units, alkyleneglycol units and polyalkylene glycol units. Soil-releasing copolyestersof the type mentioned and their use in detergents have been known forsome time. For example, DE-OS 16 17 141 describes a washing processusing polyethylene terephthalate/polyoxyethylene glycol copolymers.DE-OS 22 00 911 relates to detergents containing nonionic surfactant anda copolymer of polyoxyethylene glycol and polyethylene terephthalate.DE-OS 22 53 063 describes acidic textile finishing formulations whichcontain a copolymer of a dibasic carboxylic acid and an alkylene orcycloalkylene polyglycol and optionally an alkylene or cycloalkyleneglycol. European patent EP 066 944 relates to textile treatmentformulations containing a copolyester of ethylene glycol, polyethyleneglycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylicacid in certain molar ratios. European patent EP 185 427 describesmethyl- or ethyl-end-capped polyesters containing ethylene and/orpropylene terephthalate and polyethylene oxide terephthalate units anddetergents containing this soil-releasing polymer. European patent EP241 984 relates to a polyester containing substituted ethylene units andglycerol units in addition to oxyethylene groups and terephthalic acidunits. These soil-releasing polyesters are preferably present informulations containing multi-enzyme granules according to the inventionin quantities of 0.1% by weight to 2.5% by weight and more preferably inquantities of 0.2% by weight to 2% by weight.

A corresponding detergent or cleaning formulation may also containenzymes which have to be separately added, i.e. which are notincorporated through the multi-enzyme granules according to theinvention. However, all enzymes present are preferably incorporated inthe multi-enzyme granules.

In one preferred embodiment, a formulation in which the multi-enzymegranules according to the invention or produced in accordance with theinvention are incorporated is particulate and contains 20% by weight to55% by weight of inorganic builder, up to 15% by weight and, moreparticularly, 2% by weight to 12% by weight of water-soluble organicbuilder, 2.5% by weight to 20% by weight of synthetic anionicsurfactant, 1% by weight to 20% by weight of nonionic surfactant, up to25% by weight and, more particularly, from 1% by weight to 15% by weightof bleaching agent, up to 8% by weight and, more particularly, from 0.5%by weight to 6% by weight of bleach activator and up to 20% by weightand, more particularly, from 0.1% by weight to 15% by weight ofinorganic salts, more particularly alkali metal carbonate and/orsulfate.

In another preferred embodiment, a powder-form detergent intended inparticular for use as a light-duty detergent contains 20% by weight to55% by weight of inorganic builder, up to 15% by weight and, moreparticularly, from 2% by weight to 12% by weight of water-solubleorganic builder, from 4% by weight to 24% by weight of nonionicsurfactant, up to 15% by weight and, more particularly, from 1% byweight to 10% by weight of synthetic anionic surfactant, up to 65% byweight and, more particularly, from 1% by weight to 30% by weight ofinorganic salts, more particularly alkali metal carbonate and/or sulfateand neither bleaching agent nor bleach activator.

Another preferred embodiment is a liquid formulation containing 5% byweight to 35% by weight of water-soluble organic builder, up to 15% byweight and, more particularly, from 0.1% by weight to 5% by weight ofwater-insoluble inorganic builder, up to 15% by weight and, moreparticularly, from 0.5% by weight to 10% by weight of synthetic anionicsurfactant, from 1% by weight to 25% by weight of nonionic surfactant,up to 15% by weight and, more particularly, from 4% by weight to 12% byweight of soap and up to 30% by weight and, more particularly, from 1%by weight to 25% by weight of water and/or water-miscible solvent.

EXAMPLES Example 1

A biomass-containing fermenter broth containing around 65,000 proteaseunits per gram (PU/g) was obtained by fermentation of Bacilluslicheniformis (ATCC 53926)--modified by the process described inInternational patent application WO 91/02792 by transformation of a genesequence from Bacillus lentus DSM 5483--using the process described inGerman patent DE 29 25 427. The fermenter broth was concentrated to aprotease content of 700,000 PU/g by decantation, crossflowmicrofiltration, ultrafiltration (cutoff limit at molecular weight10,000) and subsequent concentration by evaporation in vacuo by theprocess described in International patent application WO 92/11347. 50Parts by weight of propylene glycol were then added as inhibitor. Theprimary enzyme solution was then mixed with the commercially availableliquid enzyme formulations listed in Table 1. 45 Parts by weight ofcellulose powder (Technocel® 30, a product of Cellulose FullstoffFabrik), 35 parts by weight of sucrose, 120 parts by weight of Nacarboxymethyl cellulose (Tylose®, a product of Hoechst AG), 50 parts byweight of polyethylene glycol (average molecular weight 2,000), 300parts by weight of corn starch and 130 parts by weight of wheat flourwere then added to the enzyme mixture in a mixer equipped with arotating beating tool and the resulting mixture was homogenized in anexternally cooled kneader. The plastic material was extruded in anextruder equipped with a multi-bore extrusion die (bore diameter 0.8 mm)and a rotating blade. The 0.8 mm long enzyme extrudates characterized bytheir enzyme composition in Table 1 were obtained and were then powderedwith 3 parts by weight of calcium carbonate and spheronized anddeflashed for about 1 minute in a spheronizing machine (Marumerizer®) toform uniformly rounded particles. The material leaving the spheronizerwas dried in a fluidized-bed dryer at temperatures of 40° C. to 45° C.and coated with 150 parts by weight of a coating material consisting ofTiO₂, stearyl alcohol and 40x ethoxylated castor oil. Particles smallerthan 0.4 mm and larger than 1.6 mm in size (less than 1% by weight ofall the particles) were subsequently removed by sieving.

                  TABLE 1                                                         ______________________________________                                        Enzyme Content of the Extrudates (Parts by Weight)                                       E1   E2         E3     E4                                          ______________________________________                                        Protease broth                                                                             190    190        300  190                                       Amylase.sup.a)                                                                                         --        20                                                                                  --                                   Lipase.sup.b)                                                                                        140          --                                                                                 --                                   Cellulase.sup.c)                                                                                 --                                                                                --           --                                                                                140                                   ______________________________________                                         .sup.a) Termamyl ® 300 L (liquid formulation; a product of Novo           Nordisk)                                                                      .sup.b) Lipolase ® 100 L (liquid formulation; a product of Novo           Nordisk)                                                                      .sup.c) Celluzyme ® 700 L (liquid formulation; a product of Novo          Nordisk)                                                                 

Example 2

The multi-enzyme granules E2 produced in Example 1 were mixed in aquantity of 1 part by weight with 99 parts by weight of a detergent withan apparent density of 780 g/l produced in accordance with WO 91/02047containing 18% by weight of sodium alkyl benzene sulfonate, 3% by weightof nonionic surfactant (Dehydol®), 16% by weight of sodium perborate,29% by weight of zeolite NaA, 5% by weight of sodium carbonate, 5% byweight of polymeric polycarboxylate (Sokalan CP 5, a product of BASF),6% by weight of tetraacetyl ethylenediamine, 3% by weight ofplasticizing aid (40x ethoxylated fatty alcohol) and--as the balance to100% by weight--water (formulation W1). A mixture C1 which contained thesame percentage of detergent and enzymes, but in which the two enzymeswere distributed between two separate particles (protease granulesaccording to International patent application WO 92/11347; Lipolase® 100T, a product of Novodisk) was produced for comparison. The twoformulations were stored for 6 weeks at 40° C./80% relative airhumidity. The enzyme activities (in arbitrary units) before and afterstorage are shown in Table 2 below. It can be seen that, in thedetergent containing the multi-enzyme granules according to theinvention, the stability of the enzymes present in one particle issignificantly higher than when the enzymes are present in separateparticles. The same surprising finding also applies to the multi-enzymeextrudates E1, E3 and E4 of Example 1.

                  TABLE 2                                                         ______________________________________                                        Enzyme Activities                                                                           Protease Activity                                                                        Lipase Activity                                      ______________________________________                                        W1:  Start          142          38                                                   after 6 weeks' storage                                                                       136                34                                  C1:  Start                                75117                                       after 6 weeks' storage                                                                        75                52                                  ______________________________________                                    

We claim:
 1. A process for the production of enzyme granules consistingessentially of at least two different enzymes, a competitive inhibitor,and a carrier material, comprising the steps of:A) mixing an aqueousliquid containing a first enzyme with at least one competitive inhibitorfor this enzyme to form a reversibly inactivated primary enzymecomposition; B) mixing the primary enzyme composition with at least onesecond enzyme different from the first enzyme to form an enzyme mixture;C) mixing the enzyme mixture with an inorganic carrier material, anorganic carrier material, or both; D) extruding the resulting mixturefrom step C) through a multi-bore die followed by a cutting unit; and E)if the resulting cut extrudate has a water content of more than about10% by weight, drying the resulting cut extrudate to a residual watercontent of not more than about 10% by weight.
 2. The process of claim 1wherein in step B) at least one of the at least one second enzyme isincompatible with the first enzyme.
 3. The process of claim 1 wherein instep A) the aqueous liquid containing a first enzyme is a fermentationbroth which has been freed from insoluble constituents and concentrated.4. The process of claim 1 wherein following step D) and before step E),the extrudate is spheronized.
 5. The process of claim 4 wherein theextrudate in step D) has a particle-size distribution such that lessthan about 10% by weight thereof are smaller than 0.2 mm in diameter,from about 10 to about 20% by weight are from about 0.2 to less than 0.4mm in diameter, and from about 80 to about 90% by weight are from about0.4 to less than about 0.8 mm in diameter.
 6. The process of claim 1wherein following or during step E), the extrudate particles arecontacted with materials for encapsulating and coating the particles. 7.The process of claim 1 wherein in step B) the at least one second enzymeis in the form of a mixture with a carrier material.
 8. The process ofclaim 7 wherein the carrier material in step B) comprises from about 30to about 80% by weight of an inorganic salt, from about 2 to about 40%by weight of a fibrous or powder-form cellulose, and from about 0.1 toabout 15% by weight of a binder.
 9. The process of claim 1 wherein instep A) the competitive inhibitor is at least one inhibitor selectedfrom the group consisting of a polyhydric alcohol, a lower carboxylicacid, boric acid, an alkali metal borate, a boric acid ester, a boricacid derivative, a calcium salt, a magnesium salt, and asulfur-containing reducing agent.
 10. The process of claim 1 wherein thefirst enzyme is protease and the at least one second enzyme is selectedfrom the group consisting of amylase, lipase, cellulase, hemicellulase,oxidase, peroxidase, and mixtures of the foregoing.
 11. The process ofclaim 10 wherein the protease is present in such quantity that themulti-enzyme granules obtained have a protease activity of from about50,000 PU/g to about 350,000 PU/g.
 12. The process of claim 10 whereinthe enzyme granules have an amylase activity of from about 1 KNU/g toabout 100 KNU/g.
 13. The process of claim 10 wherein the enzyme granuleshave a lipase activity of from about 1 KLU/g to about 80 KLU/g.
 14. Theprocess of claim 10 wherein the enzyme granules have a cellulaseactivity of from about 50 CEVU/g to about 1250 CEVU/g.
 15. The processof claim 1 wherein in step C) the carrier material is at least onecarrier material selected from the group consisting of cellulose,maltodextrose, sucrose, invert sugar, glucose, a starch, a cereal flour,a cellulose ether, an alkali metal alumosilicate, a layer silicate, anda water-soluble inorganic or organic salt.
 16. The process of claim 1wherein in step E) the extrudate has a water content of from about 5 toabout 8% by weight.
 17. The process of claim 1 wherein the carriermaterial in step C) comprises from about 20 to about 80% by weight of astarch, and from about 10 to about 35% by weight of a cereal flour,based on the weight of the carrier material.
 18. The process of claim 17wherein the total weight of starch and cereal flour is from about 60 toabout 95% by weight of the carrier material.
 19. The process of claim 1wherein the extrudate in step D) has a length-to-thickness ratio of fromabout 0.9:1 to about 1.1:1.
 20. The enzyme granules produced by theprocess of claim
 1. 21. In a detergent or cleaning composition, theimprovement wherein the composition contains from about 0.1 to about 5%by weight of the enzyme granules produced by the process of claim
 1. 22.The detergent or cleaning composition of claim 21 wherein thecomposition contains from about 0.5 to about 2.5% by weight of theenzyme granules.
 23. A process for the production of enzyme granulescontaining at least two different enzymes comprising the steps of:A)mixing an aqueous liquid containing a first enzyme with a reversiblecompetitive inhibitor for this enzyme to form a primary enzymecomposition; B) mixing the primary enzyme composition with at least onesecond enzyme different from the first enzyme; and wherein the at leastone second enzyme is in the form of a mixture with an inorganic carriermaterial, an organic carrier material, or both; C) extruding theresulting mixture from step B) through a multi-bore die followed by acutting unit; and D) if the resulting cut extrudate has a water contentof more than about 10% by weight, drying the resulting cut extrudate toa residual water content of not more than 10% by weight.
 24. In adetergent or cleaning composition, the improvement wherein thecomposition contains from about 0.1 to about 5% by weight of the enzymegranules produced by the process of claim 23.